Dumbbell-Shaped, Block-Graft Copolymer with Aligned Domains for High-performance Hydrocarbon Polymer Electrolyte Membranes.

Abstract

Given the environmental concerns surrounding fluoromaterials, the use of high-cost perfluorinated sulfonic acids (PFSAs) in fuel cells and water electrolysis contradicts the pursuit of clean energy systems. Herein, we present a fluorine-free dumbbell-shaped block-graft copolymer, derived from the cost-effective triblock copolymer poly(styrene-b-ethylene-co-butylene-b-styrene) (SEBS), for polymer electrolyte membranes (PEMs). This unique polymer shape led to the alignment of the hydrophobic-hydrophilic domains along a preferred orientation, resulting in the construction of interconnected proton channels across the membrane. A bicontinuous network allowed efficient proton transport with reduced tortuosity, leading to an exceptional ionic conductivity (249 mS cm-1 at 80 °C and 90% relative humidity (RH)), despite a low ion exchange capacity (IEC; 1.41). Furthermore, membrane-electrode assembly (MEA) prepared with our membrane exhibited stable performance over a period of 150 h at 80 °C and 30% RH. This study demonstrates a novel polymer structure design and highlights a promising outlook for hydrocarbon PEMs as alternatives to PFSAs.